Polyglycidyl compounds containing n-heterocyclic structure

ABSTRACT

The polyglycidyl compounds according to the invention can be manufactured by reacting epihalogenohydrin with compounds of the formula IV ##STR1## or the formula V ##STR2## in which 1. N DENOTES 2, 3 OR 4, 
     2. A represents a 2-valent, 3-valent or 4-valent organic radical which either contains a N-heterocyclic or cycloaliphatic ring or 2 N-heterocyclic rings or 2-phenylene rings, 
     3. either B denotes the --CH 2 .O.CO-- radical and m denotes the number 1, or B denotes the radical ##STR3## and m denotes O, and 4. R 1  represents a divalent radical, which contains at least one hydrantoin ring or uracil ring. 
     During the reaction hydrogen halide splits off. From curable mixtures containing polyglycidyl compounds according to the invention and a curing agent such as hexahydrophthalic anhydride or phthalic anhydride are obtained products with good mechanical and electrical properties.

This is a Divisional of application Ser. No. 371,449 filed on June 19,1973 now U.S. Pat. No. 3,900,493 which issued on Aug. 19, 1975.

The invention relates to new polyglycidyl compounds containingN-heterocyclic structures, a process for their manufacture and theiruse.

Heterocyclic compounds which contain glycidyl groups are known, forexample from German Offenlegungsschriften 1,932,305 and 1,932,306 andfrom French Patent Specification 1,394,438 and Swiss PatentSpecification 345,347. The process products hitherto known frequentlypresent problems with regard to storage and are not always easy toprocess. Furthermore, the cured products frequently do not meet thestandards set with regard to mechanical and electrical properties.

The subject of the invention are new polyglycidyl compounds containingN-heterocyclic structures, of the general formula I ##STR4## in which 1.N DENOTES 2, 3 OR 4,

2. A represents a 2-valent, 3-valent or 4-valent organic radical whicheither contains a N-heterocyclic or cycloaliphatic ring or 2N-heterocyclic rings or 2 phenylene rings, and

3. R¹ represents a divalent radical of the formula II ##STR5## in whicha and b are identical or different and denote either 0 or 1, and inwhich R³ denotes a hydrogen atom or a methyl group and R² denotes anitrogen-free, 2-valent radical which is necessary to complete afive-membered or six-membered unsubstituted or substituted ring, or ofthe general formula III ##STR6## in which 1. either B denotes the--CH₂.O.CO-- radical and m denotes the number 1, or B denotes theradical ##STR7## and m denotes 0, and 2. R¹ has the above meaning.

In the formula I, A can represent one of the following organic moleculargroups: ##STR8##

In the formula II, R² can denote one of the radicals ##STR9## In such acase, the polyglycidyl compounds according to the formula I or formulaIII are substances containing hydantoin rings.

R² can, however, also represent one of the following divalent radicals:##STR10## If this is the case, the polyglycidyl compounds according tothe formula I or formula III are substances which contain rings whichare derived from uracil or barbituric acid.

The new polyglycidyl compounds containing N-heterocyclic structures canbe manufactured according to the invention in an elegant manner byreacting compounds of the formula IV ##STR11## or the formula V##STR12## in which A, R¹, B, n and m have the abovementioned meaning,with epihalogenohydrin, hydrogen halide being split off. Instead ofepihalogenohydrin, methylepihalogenohydrin can also be employed. In thatcase, polyglycidyl compounds are obtained which are slightly modified bythe methyl groups introduced into the molecule. Preferably,epichlorohydrin is employed.

The process according to the invention is advantageously carried outwith azeotropic removal of the water in the presence of a hydrogenhalide acceptor. As such it is possible to use, for example, alkalimetal hydroxide, most simply sodium hydroxide in an equivalent amount orin slight excess (5 - 30%). If desired, a catalyst is also employed, forexample a quaternary ammonium halide, such as tetramethyl-ammoniumhydroxide, tetraethylammonium bromide or benzyltri-methylammoniumchloride.

It is surprising that the process according to the invention can becarried out without complications. Given the presence of the numerousactive H atoms in the reaction mixture and the accumulation of theepoxide groups in the molecule of the resulting end product of theformula I or III, complications due to undesired polyaddition andpremature crosslinking were to be expected.

The starting substances of the formula IV or of the formula V for themanufacture of the polyglycidyl compounds according to the invention arealso new. They are substances which always contain at least 2 (namely n)secondary hydroxyl groups. In addition, they either contain n >NH groupsof a N-heterocyclic ring and n primary hydroxyl groups.

The manufacture of these new polyols of the formula IV or of the formulaV takes place, in the former case, by reaction of appropriate diepoxide,triepoxide or tetraepoxide compounds with H-heterocyclic substances ofthe formula ##STR13## in which R² and a are defined as above, to givethe corresponding adduct in a manner which is in itself known, therebeing about 2 >NH groups in the reaction mixture per 1 epoxide group.

In the latter case, in which the substances of the formula IV or of theformula V also contain primary hydroxyl groups in addition to thesecondary hydroxyl groups, an identical adduct to that in the first caseis initially manufactured as an intermediate product. In a 2nd stage,the >NH groups contained in this adduct are then reacted further withethylene oxide or propylene oxide in a known manner to give theparticular primary alcohol.

The following may be mentioned as examples of polyepoxide compoundswhich are suitable for use as starting products for the polyols of theformula IV:1-glycidyl-3-(glycidyl-2'-oxy-n-propyl)-5,5-dimethylhydantoin,1-glycidyloxymethyl-3-glycidyl-5,5-dimethylhydantoin,1,1'-methylene-bis-(3-glycidyl-5,5-dimethylhydantoin),1,3-diglycidyl-5,5-dimethylhydantoin,2,2,6,6-tetra(glycidylcarboxy-ethyl)-cyclohexanone, bisphenol-Adiglycidyl ether or polymeric derivatives thereof. (As regards thepolymeric derivatives of bisphenol-A diglycidyl ethers, it shouldadditionally be noted that for practical purposes appropriate polymermixtures with degrees of polymerisation of up to about 5 are concerned).

As polyepoxide compounds which are suitable for use as starting productsfor the polyols of the formula V, the following should be listed asexamples: 3,4-epoxycylohexylmethyl)-3,4-epoxycyclohexanecarboxylate and3-(3',4'-epoxycyclohexyl)-2,4-dioxaspiro-(5,5)-9,10-epoxyundecane.

The following N-heterocyclic substances are examples of reactionpartners for these polyepoxide compounds in the manufacture of the abovepolyols: 5,5-pentamethylenehydantoin, 5,5-dimethylhydantoin,5-isopropylhydantoin, 5,5-diethylbarbituric acid,1,1'-methylene-bis-(5,5-dimethyl-5,6-dihydrouracil),1,1'-methylene-bis-(5,5-dimethylhydantoin),1,1'-methylene-bis-(5-isopropylhydantoin), 6-methyluracil,5,5-dimethyl-6-isopropyl-5,6-dihydrouracil and1,2-bis-(5,5-dimethylhydantoinyl-3)-ethane.

These new polyols which may contain >NH groups are viscous or solid, inmost cases pale yellow-coloured, substances. If these are derived frompolymeric bisphenol-A diglycidyl ethers, the reaction with theepihalogenohydrin leads either to polyglycidyl compounds of the formulaI which still contain, unchanged, the OH groups originating from theinitial diglycidyl ethers, or to polyglycidyl compounds which containadditional epoxide groups produced by reaction of these originallypresent OH groups with epihalogenohydrin. Furthermore, intermediatestages are also possible. The degree of reaction of the original OHgroups results essentially from the amount of the epihalogenohydrin adcaustic alkali in the reaction mixture. Usable polyglycidyl compounds ofthe formula (I) according to the invention are also obtained by startingfrom compounds of the formula IV in which the radical A denotes themolecular group of the formula ##STR14## or the molecular group of theformula ##STR15## Starting substances for these special compounds of theformula IV are again the diglycidyl ethers of resorcinol or ofpolyethers containing several resorcinol structures.

The polyglycidyl compounds according to the invention, of the formula Iand the formula III, are solid or liquid, mostly pale yellow-coloured,substances. The special feature of these substances is that they containa relatively large number of glycidyl groups per molecule. They haveepoxide contents of between about 3.0 and 8.0 mols/kg of resin and can,together with curing agents, such as dicarboxylic acid anhydrides,easily be converted into curable mixtures at temperatures of 60° - 160°C. Hexahydrophthalic anhydride and phthalic anhydride are particularysuitable as curing agents.

The curing of these mixtures, which is a further subject of thisinvention, in general takes place at temperatures of 80° to 170° C. Itcan also be carried out stepwise at different temperatures. Ultimately,mouldings of high mechanical and electrical quality are obtained. Thecurable mixtures according to the invention are in particular suitablefor use as compression moulding compositions and casting resins. Inprinciple, they can also be used as lacquer resins and laminatingresins.

For the manufacture, modification or processing and the like, everythingknown to the expert from publications and relevant patent specificationson an extensive scale applies to the mixtures according to theinvention.

In the examples which follow, parts denote parts by weight and thepercentages denote percentages by weight. The relationship of parts byvolume to parts by weight is as of ml to g.

A. MANUFACTURING EXAMPLES Manufacture of the Starting Substancesaccording to the Formula IV or V EXAMPLE A Adduct of5,5-dimethylhydantoin and1,1'-methylene-bis-(3-glycidyl-5,5-dimethylhydantoin)

256 g of 5,5-dimethylhydantoin (2 mols) and 1.6 ml of 40% strengthaqueous tetramethylammonium chloride solution are heated to 170° C in aglass apparatus equipped with a stirrer, thermometer and refluxcondenser and the resulting melt is stirred. 380 g of1,1'-methylene-bis-(3-glycidyl-5,5-dimethylhydantoin) (5.0 equivalent ofepoxide) are added over the course of 1 hour, whilst stirring. 3 hourslater, the residual epoxide content is only 0.14 equivalent/kg. Themixture is stirred for a further 5 hours at 190° C and the adduct ispoured out onto a metal sheet. A solid, clear, brittle mass of softeningpoint 116° C is obtained in quantitative yield. The residual epoxidecontent is only 0.048 equivalent/kg (corresponding to 98.3% conversion).

The content of >NH groups in the 3-position of the N-heterocyclic ringis 0.17 equivalent/kg (corresponding to a conversion of 94.3% oftheory). Accordingly, the product predominantly consists of: ##STR16##

EXAMPLE B Adduct of 5,5-dimethylhydantoin and bisphenol-A-diglycidylether

A solution of 177 g of a technically manufactured bisphenol-A diglycidylether (Araldite MY 790) of high monomer content (5.70 epoxideequivalents/kg) (corresponding to 0.5 mol) in 500 ml ofdimethylformamide is mixed with 128.2 g of 5,5-dimethylhydantoin (1 mol)and the mixture is heated to 120° C whilst stirring. 1.7 g oftetraethylammonium chloride are then added, whereupon a slightlyexothermic reaction commences. In the course thereof, the temperaturerises to 130° C. Thereafter, the mixture is stirred for a further 2hours at 120° C adjusted to pH=7 with a little 50% strength sulphuricacid, filtered hot and concentrated at 75° C/15 mm Hg. Thereafter theresidue is dried to constant weight at 90° C/0.2 mm Hg. A solid, clear,light yellow adduct is obtained in quantitative yield. This crude adductcan be purified by recrystallisation from 50% strength ethanol in theratio 1:6. After drying, 269.8 g (88.4% of theory) of a colourless finecrystalline material which melts at 169° - 182° C is obtained. The NMRand IR spectra shown that predominantly an adduct of the followingstructure is present: ##STR17##

EXAMPLE C Adduct of methylene-bis-dimethylhydantoin and bisphenol-Adiglycidyl ether

117.5 g of the bisphenol-A diglycidyl ether used in Example 2 (0.3 mol)in 700 ml of dimethylformamide are reacted with 160 g of1,1'-methylene-bis(5,5-dimethylhydantoin) (0.6 mol) at 120° - 124° C,analogously to Example b. 0.9 g of tetraethylammonium chloride is usedas the catalyst. The reaction is again slightly exothermic. Afterstirring for 3 hours at 120° C, the mixture is worked up according toExample B.

320 g of a yellowish, viscous resin, which is completely dried in vacuoat 70° C, are obtained. A crude product which, according to NMR, agreeswith the structure shown below, is obtained. The elementary analysis ofthe crude product shows:

    ______________________________________                                        Found            Calculated                                                   ______________________________________                                        58.6% C          58.9% C                                                      6.8% H           6.4% H                                                       12.8% N          12.8% N                                                      ______________________________________                                    

This product was again processed as it stands. ##STR18##

EXAMPLE D Adduct of 5,5-dimethylhydantoin and(3,4-epoxycyclohexyl-methyl)-3,4-epoxycyclohexanecarboxylate

A solution of 128 g of technically manufactured(3,4-epoxy-cyclohexylmethyl)-3,4-epoxycylohexanecarboxylate(corresponding to 0.5 mol) in 300 ml of dimethylformamide is mixed, at120° C, with 1.7 g of tetraethylammonium chloride and 128.1 g of5,5-dimethylhydantoin (1.0 mol). The solution is stirred for 10 hours at135° C and is worked up as described in Example B. A clear, lightochre-coloured product is obtained in quantitative yield; it can easilybe powdered and essentially corresponds to the following structure:##STR19##

EXAMPLE E Adduct of 1,1'-methylene-bis-dimethylhydantoin and(3,4-epoxycyclohexylmethyl)-3,4-epoxycylohexanecarboxylate

Analogously to Example D, 384 g of the epoxide resin used in Example D,in 2,000 ml of dimethylformamide, are reacted with 804.8 g of1,1'-methylene-bis-(5,5-dimethyl)-hydantoin, using 5 g oftetraethylammonium chloride as the catalyst. The reaction is carried outanalogously to Example D. Working up takes place as follows: The hotsolution is filtered into an Erlenmeyer flask and is left to stand at25° C. After some hours, the adduct begins to crystallise out. Themixture is cooled to 5° C whilst stirring and 500 ml of water are added,whereby a thick crystal paste results. This is filtered and the productis suction-dried, and then dried to constant weight at 70° C under 25 mmHg. A pale yellow crystal powder is obtained, the yield being 1,048 g(corresponding to 88.1% of theory).

EXAMPLE F Adduct of bisphenol-A diglycid and5,5-dimethyl-6-iso-propyl-5,6-dihydrouracil

A mixture of 177 g of the bisphenol-A diglycidyl ether used in Example B(0.5 mol), 184.2 g of 5,5-dimethyl-6-isopropyl-5,6-dihydrouracil (1 mol)and 0.5 g of 50% strength sodium hydroxide solution is heated to 150° Cwhilst stirring.

The mixture is kept at this temperature for 6 hours and is then pouredout onto a metal sheet to cool.

345 g of a clear, pale yellow, brittle glass (95.6% of theory) areobtained, of residual epoxide content 0.08 equivalent/kg. The productconsists essentially of the adduct of the following formula: ##STR20##

EXAMPLE G Adduct of higher-molecular bisphenol-A diglycidyl ether and5,5-dimethyl-6-isopropyl-5,6-dihydrouracil

A mixture of 190 g of a commercially available higher-molecularbisphenol-A glycidyl ether resin with 2.7 epoxide equivalents/kg(Araldite B), 94 g of 5,5-dimethyl-6-isopropyl-5,6-dihydrouracil and 0.5ml of 50% strength sodium hydroxide solution is reacted at 150° C,whilst stirring. After 1.5 hours, a sample taken from the batch shows anepoxide content of 0.39 equivalent/kg. The mixture is then stirred for afurther 3 hours at 165° C, in the course of which the epoxide contentdrops to below 0.1 equivalent/kg. The adduct is poured out onto a metalsheet to cool. An adduct mixture of predominantly the followingstructure is obtained: ##STR21## In this formula, n denotes the averagedegree of polymerisation (also of the initial epoxide resin) of about 6.

EXAMPLE H Addition of ethylene oxide to the product from Example B

220 g of the adduct manufactured according to Example B (0.361 mol) and1.4 g of lithium chloride are dissolved in 540 ml of dimethylformamide.A solution of 43.7 g of ethene oxide (0.992 mol) in 250 ml ofdimethylformamide is added to the first solution at room temperature,whilst stirring gently. The mixture is warmed to 100° C over the courseof 2 hours and stirred for a further 3 hours at this temperature.Thereafter it is cooled to 50° C, filtered and concentrated at 80° C/20mm Hg, and dried to constant weight at 95° C/0.1 mm Hg. 250 g of aclear, highly viscous, light ochre-coloured polyol (100% of theory) areobtained, of which the NMR spectrum agrees with predominantly thefollowing structure: ##STR22##

EXAMPLE I Addition of ethylene oxide to the product from Example C

Analogously to Example H, a solution of 200 g of the adduct manufacturedaccording to Example C and 1.0 g of lithium chloride in 500 ml ofdimethylformamide is treated, at room temperature, with a solution of27.5 g of ethylene oxide in 100 ml of dimethylformamide and theprocedure described in Example H is followed.

190 g of a clear glassy tetraalcohol (95% of theory) are obtained andare glycidylated in the crude form.

EXAMPLE J Addition of ethylene oxide to the product from Example D

676 g of the adduct manufactured according to Example D are dissolved in1,300 ml of dimethylformamide. After addition of 1.7 g of lithiumchloride, 234.5 g of ethylene oxide in 600 ml of dimethylformamide areadded and the procedure analogous to Example H is followed. 690 g of aproduct (87%) are obtained, in which the N--H groups of the formulagiven in Example D are very largely replaced by the structure --N--CH₂--CH₂ --OH.

EXAMPLE K Adduct of 2 mols of 5,5-diethylbarbituric acid and 1 mol of3-(3',4'-epoxycylohexyl)-2,4-dioxaspiro-(5,5)-9,10-epoxyundecane

A solution of 64.3 g of technically manufactured3-(3',4'-epoxycylohexyl)-2,4-dioxaspiro-(5,5) -9,10-epoxyundecane (93.6%strength) (0.226 mol) and 0.75 g of 50% strength aqueoustetramethylammonium chloride in 250 ml of dimethylformamide is stirredat 118° C. The clear, colourless solution is mixed with 83.1 g ofdiethylbarbituric acid (0.452 mol) over the course of 15 minutes. Thismixture is stirred for a further 10 hours at 117°-119° C and the solventis then distilled off in vacuo. 146 g of a brown, brittle product areobtained, which melts at 67.2° C (Mettler FP 51) and has the followingstructure: ##STR23##

EXAMPLE L Adduct of 1,3-diglycidyl-5,5-dimethylhydantoin and5,5-dimethylhydantoin

390.9 g of technically manufactured 1,3-diglycidyl-5,5-dimethylhydantoin(92.5% strength) (1.5 mols) and 5.0 g of tetraethylammonium chloride aredissolved in 750 ml of dimethylformamide and this solution is stirred at110° C. 384.5 g of 5,5-dimethyl-hydantoin (3.0 mols) are then added withvigorous stirring. The reaction becomes strongly exothermic so that theheating bath is removed and replaced by an ice water bath; thetemperature is thus regulated to 102° - 112° C. When the exothermiceffect has subsided, the mixture is stirred for a further 3 hours at115° C. The solvent is then distilled off at 100° C/30 mm Hg and theproduct is dried at 100° C/0.2 mm Hg. 765 g of a pale yellow, brittleglass, which can easily be powdered, are obtained.

EXAMPLE M Adduct of 5-isopropylhydantoin and1-glycidyl-3-glycidyl-2'-oxy-n-propyl-5,5-dimethylhydantoin (molar ratio2:1).

335 g of technically manufactured1-glycidyl-3-glycidyloxypropyl-5,5-dimethylhydantoin (epoxide content5.97 equivalents/kg) (1 mol) and 3.3 g of tetraethylammonium chlorideare dissolved in 1 liter of dimethylformamide and 258.2 g of5-isopropylhydantoin (2 mols) are added at 120° C, whilst stirring. Thereaction becomes exothermic and the mixture is kept at 120° C for atotal of 5 hours by periodic cooling. Working up takes place analogouslyto Example 11. 593 g (theory: 583 g) of a light brown powder, melting at48.6° C (Mettler FP 51) are obtained. The elementary analysis of thecrude product shows:

    ______________________________________                                        Found            Calculated                                                   ______________________________________                                         7.3 % H          7.3 % H                                                     13.9 % N         14.4 % N                                                     ______________________________________                                    

According to the H-NMR spectrum, the crude product only retains a traceof dimethylformamide.

The product has the following structure: ##STR24##

EXAMPLE N Adduct of 1,1'-methylene-bis-(5,5-dimethyl-5,6-dihydrouracil)and 1-glycidyloxymethyl-3-glycidyl-5,5-dimethylhydantoin (molar ratio2:1)

A solution of 22.2 g of1-glycidyloxymethyl-3-glycidyl-5,5-dimethylhydantoin (97.3% strength)(0.077 mol) and 0.2 g of tetraethylammonium chloride in 80 ml ofdimethylformamide is mixed, at 120° C, with 45.6 g of1,1'-methylene-bis(5,5-dimethyl-5,6-dihydrouracil) (0.154 mol). Thereaction, and working up, take place analogously to Example K.

44 g of the corresponding adduct are obtained in the form of a lightpowder (66.7% of theory).

EXAMPLE O Adduct of 1,1'-methylene-bis(5,5-dimethylhydantoin) and1,1'-methylene-bis(3-glycidyl-5,5-dimethylhydantoin)

A mixture of 205.5 g of1,1'-methylene-bis-(3-glycidyl-5,5-dimethylhydantoin) (4.9 epoxideequivalents/kg) (0.54 mol), 289.8 g of1,1'-methylene-bis(5,5-dimethyl-hydantoin) (1.08 mols), 1.8 g oftetraethylammonium chloride and 750 ml of dimethylformamide is stirredat 110°-120° C; the reaction becomes exothermic and is carried outaccording to Example K, and the product is worked up according toExample K.

488 g of a light yellow powder (98.6% of theory) are obtained.

EXAMPLE P Adduct of 6-methyluracil and1,1'-methylene-bis-(3-glycidyl-5,5-dimethylhydantoin)

A mixture of 76.1 g of the1,1'-methylene-bis-(3-glycidyl-5,5-dimethylhydantoin) (0.2 mol) used inExample N, 0.6 g of tetraethylammonium chloride and 50.5 g of6-methyluracil (0.4 mol) is stirred for 10 hours at 120° C, whereby aclear, colourless solution is produced; this is worked up analogously toExample k.

127 g (100% of theory) of a light yellow, glassy substance are obtained.This can be recrystallised from alcohol. 104 g (82.2% of theory) of finecrystals, melting at 176° C (Mettler FP 51) are obtained.

EXAMPLE Q Adduct of 5,5-dimethylhydantoin and 2,2,6,6-tetra(glycidylcarboxy-ethyl)cyclohexanone

123.8 g of 2,2,6,6-tetra(glycidyl-carboxy-ethyl)-cyclohexanone (epoxidecontent: 5.9 equivalents/kg) (0.184 mol), 94.1 g of5,5-dimethylhydantoin and 200 ml of dimethylformamide are stirred for 5hous at 125°-130° C; the reaction is initially slightly exothermic. Theworking up of the product takes place analogously to Example K. 210 g ofa highly viscous liquid are obtained; this crude product still containsa trace of dimethylformamide.

EXAMPLE R 2:1 adduct of 1,3-diglycidyl-5,5-dimethyl-hydantoin andhydrogenated bisphenol-A

The following mixture is stirred for 4.5 hours at 120° C: 512.8 g of1,3-diglycidyl-5,5-dimethylhydantoin (2.0 mols), 240.4 g of hydrogenatedbisphenol A (1.0 mol), 3.0 g of lithium chloride and 2 l ofdimethylformamide.

After the customary working up by distilling off the solvent, anddrying, 746 g (103% of theory; the product still contains traces ofdimethylformamide) of a light ochre-coloured melt, which crystallises,are obtained. This crude product (diglycidyl compound) has an epoxidecontent of 2.49 equivalents/kg (89.8% of theory) and is employed,without further purification, for the manufacture of the tetraglycidylcompound.

EXAMPLE S 2:1 adduct of 5,5-dimethylhydantoin and the diglycidyl etherof hydrogenated bisphenol A

A mixture of 454.6 g of technically manufactured diglycidyl ether ofhydrogenated bisphenol A, having an epoxide content of 4.4equivalents/kg (1.0 mol), 256.3 g of 5,5-dimethylhydantoin, 2.5 g oflithium chloride and 1.5 l of dimethylformamide is stirred for 4 hoursat 130°-140° C. Thereafter it is filtered and completely concentrated at80° C under a water pump vacuum, and the residue is then dried for 1.5hours at 80° C/0.6 mm Hg.

A light yellow, clear, resinous adduct is obtained, which no longercontains any epoxide and still contains a little dimethylformamide;yield 750.5 g.

Manufacture of the polyglycidyl compounds according to the inventionEXAMPLE 1

A mixture of 63.6 g of the adduct manufactured according to Example A(0.1 mol; 0.4 equivalent of reactive H), 370 g of epichlorohydrin and0.3 g of tetramethylammonium chloride is stirred for 140 minutes at117°-118° C. A sample withdrawn from the batch and freed of all volatileconstituents then contains 1.88 epoxide equivalents/kg.

The dehydrochlorination is carried out as follows: An azeotropiccirculatory distillation is set up, by application of vacuum (60-90 mmHg) in such a way that a vigorous distillation proceeds in the reactionmixture at 60° C. 38.4 g of 50% strength sodium hydroxide solution (0.48mol) are now added dropwise over the course of 150 minutes, whilststirring vigorously. In the course thereof, the water present in thereaction mixture is continuously removed from the batch, and separatedoff. Thereafter, distillation is allowed to continue for a further 15minutes, the residue is cooled to 30° C, and the sodium chlorideproduced in the reaction is filtered off. The filtrate is then washedwith 50 ml of water to remove the last traces of caustic alkali and saltand the organic phase is concentrated on a rotary evaporator at 60° C/15mm Hg. 50 ml of water are now added and traces of epichlorohydrin andthe like are distilled off together with this water. Thereafter, thesame process is repeated with 50 ml of toluene to remove remnants ofwater. The residue is then treated at 120° C/0.2 mm Hg until it reachesconstant weight.

82.7 g (96.2% of theory) of a brittle, clear, pale yellow resin ofepoxide content 4.30 equivalents/kg (92.7% of theory) are obtained. Thetotal chlorine content is 1.1%. The new tetraglycidyl compound has asoftening point of 66° C (according to Kofler) and essentially ispresent in the following structure: ##STR25##

EXAMPLE 2 Glycidylation of the adduct according to Example B

Analogously to Example 1, 503 g of the adduct manufactured according toExample B (0.84 mol) are stirred with 2,495 g of epichlorohydrin (26.97mols) and 5.6 g of tetraethylammonium chloride for 3 hours at 90° C.Thereafter, dehydrochlorination is carried out, as described in Example1), with 350.5 g of 50% strength sodium hydroxide solution, underazeotropic circulatory distillation and whilst stirring vigorously.Working up and purification are also carried out analogously toExample 1. 632 g (97% of theory) of a very viscous tetraglycidylcompound are obtained, of epoxide content 4.26 epoxide equivalents/kg(86.4% of theory).

EXAMPLE 3 Glycidylation of the adduct according to Example I

179.8 g of the crude tetraalcohol manufactured according to Example I(0.186 mol) are treated with 552 g of epichlorohydrin (5.967 mols) and0.9 g of tetraethylammonium chloride analogously to Example A. Thedehydrochlorination is carried out with 77.8 g of 50% strength sodiumhydroxide solution, again as described. After working up andpurification analogously to Example 1, 189.2 g of a very viscous, clear,light yellow tetraglycidyl compound (94% of theory) are obtained, ofwhich the epoxide content is 3.4 epoxide equivalents/kg (100% oftheory). The total chlorine content is 2%.

EXAMPLE 4 Glycidylation of the adduct according to Example J

656.5 g of the tetraalcohol obtained according to Example J (1.1 mols)and 4 g of tetraethylammonium chloride in 3,330 g of epichlorohydrin(36.0 mols) are treated analogously to Example 1. Thedehydrohalogenation is carried out with 456.6 g of 50% strength aqueoussodium hydroxide solution (5.71 mols) in the manner described above. Theworking up again takes place analogously to Example A. 704 g (78% oftheory) of the desired tetraglycidyl compound, of which the epoxidecontent is 4.69 epoxide equivalents per kg (95.8% of theory), areobtained. The total chlorine content is 1.6%. The nitrogen content is6.7% (theory, 6.9%)

EXAMPLE 5 Glycidylation of the adduct from Example E

789 g of the adduct manufactured according to Example E (1 mol) togetherwith 6.6 g of tetraethylammonium chloride are treated with 2,950 g ofepichlorohydrin according to Example 1. Both the dehydrochlorinationwith 410 g of 50% strength aqueous sodium hydroxide solution and thesubsequent working up are also carried out according to Example 1. 951 g(95% of theory) of a solid, clear resin with 3.32 epoxide equivalents/kg(82.6% of theory) are obtained. The softening range is about 92° C.

EXAMPLE 6 Glycidylation of the adduct from Example F

As described in Example 1, 345 g of the adduct from Example F, 3.2 g oftetraethylammonium chloride, 1,420 g of epichlorohydrin and 199.5 g of50% strength aqueous sodium hydroxide solution are reacted, and workedup, under the conditions described.

383.2 g of the desired tetraglycidyl compound (94.8% of theory),containing 4.08 epoxide equivalents/kg (86% of theory), are obtained.The softening point is about 58° C.

EXAMPLE 7 Glycidylation of the adduct from Example G

182 g of the adduct manufactured according to Example G are treated with1.3 g of tetraethylammonium chloride and 1,200 g of epichlorohydrinaccording to Example 1. The dehydrochlorination with 67.3 g of 50%strength aqueous sodium hydroxide solution, and the further working up,also take place as described above.

216.2 g of a solid resin (99% of theory) with an epoxide content of 3.8equivalents/kg are obtained.

EXAMPLE 8 Tetraglycidyl compound of the product according to Example H

Analogously to Example 1, a solution of 139.4 g of the tetraalcoholmanufactured according to Example H (0.2 mol) is reacted with 444 g ofepichlorohydrin (4.8 mols) and 0.9 g of tetraethylammonium chloride byfirst stirring for 2 hours at 90° C.

Dehydrohalogenation is then carried out with 83.5 g of 50% strengthsodium hydroxide solution under azeotropic circulatory distillation, asdescribed in more detail in Example 1. The working up and purificationof the product take place according to Example 1.

170.7 g of a yellow, clear, viscous resin (93.9% of theory), of epoxidecontent 4.35 equivalents/kg (98.9% of theory), are obtained. The totalchlorine content is 1.5%.

EXAMPLE 9 Tetraglycidyl compound of the product according to Example K

A solution of 137.7 g of the adduct manufactured according to Example K,of melting point 67.2° C (0.217 mol) and 1.9 g of 50% strength aqueoustetramethylammonium chloride solution in 642 g of epichlorohydrin (6.94mols) is treated analogously to Example 1. The dehydrohalogenation alsotakes place according to Example 1, with 79.9 g of 50% strength aqueoussodium hydroxide solution (0.998 mol). After working up analogously toL, 135.4 g (72.6% of theory) of a yellow, practically solid (softeningpoint about room temperature) tetraglycidyl compound of epoxide content4.57 equivalents/kg (98.1% of theory) are obtained. Analytical data:

    ______________________________________                                        Found            Calculated (C.sub.43 H.sub.62 N.sub.4 O.sub.14)              ______________________________________                                        7.4 % H          7.3 % H                                                      6.7 % N          6.5 % N                                                       1.4 % Cl         0.0 % Cl                                                    ______________________________________                                    

EXAMPLE 10 Tetraglycidylation of the product according to Example L

621 g of the adduct manufactured according to Example L (1.25 mols) aretreated analogously to Example L with 3,700 g of epichlorohydrin, 10 gof 50% strength aqueous tetramethylammonium chloride solution and thenwith 460 g of 40% strength aqueous sodium hydroxide solution (5.75mols); the working up of the product is carried out appropriately.

762.2 g (84.6% of theory) of a brown tetraglycidyl compound with 4.96epoxide equivalents/kg (89.3% of theory) and 1.2% of total chlorine,which softens at room temperature, are obtained.

EXAMPLE 11 Tetraglycidylation of the product according to Example M

The following substances are reacted analogously to Example 1: 563.0 gof the adduct from Example M (0.966 mol), 2,860 g of epichlorohydrin(30.9 mols), 8.5 g of 50% strength aqueous tetramethylammonium chlorideand 356 g of 50% strength aqueous sodium hydroxide solution.

Working up takes place as described above and a highly viscous brownresin, of epoxide content 4.37 equivalents/kg (88.1% of theory), isobtained in 92% yield (715.7 g); the total chlorine content is 2%.

EXAMPLE 12 Tetraglycidylation of the product according to Example N

The following are reacted analogously to Example 1: 36 g of the adductfrom Example N (0.042 mol), 124 g of epichlorohydrin (1.34 mols), 0.7 gof 50% strength aqueous tetramethylammonium chloride and 15.4 g of 50%strength aqueous sodium hydroxide solution (0.19 mol).

After the customary working up, 28 g (62%) of a light brown, tacky resinare obtained. Epoxide content 3.08 equivalents/kg (83% of theory).

EXAMPLE 13 Tetraglycidylation of the product according to Example O

The following are reacted according to Example 1: 0.315 mol of adductaccording to Example O (289 g), 10 mols of epichlorohydrin (925 g), 2.8g of 50% strength aqueous tetramethylammonium chloride and 1.45 mols of50% strength sodium hydroxide solution (116 g). Working up takes placeas mentioned and a light yellow, solid tetraglycidyl compound isobtained, of softening point 67° C (according to Kofler). The epoxidecontent is 3.71 equivalents/kg (94.6% of theory).

EXAMPLE 14 Tetraglycidyl compound of the product according to Example C

The following were reacted analogously to Example 1: 444.6 g of adduct,manufactured according to Example C (0.5 mol), 1,480 g ofepichlorohydrin (16 mols), 8.8 g of 50% strength aqueoustetramethylammonium chloride and 184 g of 50% strength sodium hydroxidesolution (2.3 mols).

The product is isolated according to Example 1 and 441.4 g (81%) of asolid, light brown resin are obtained, softening at 78° C (Kofler) andhaving an epoxide content of 3.41 equivalents/kg (93.9% of theory).

EXAMPLE 15 Tetraglycidyl compound of the product according to Example P

The following are reacted analogously to Example 1: 72.0 g of the adductaccording to Example P (0.114 mol), 474.0 g of epichlorohydrin (5.125mols), 4.6 g of tetramethyl-ammonium chloride, 50% strength in water and42.4 g of 50% strength aqueous sodium hydroxide solution (0.53 mol).

The customary working up yields 76.0 g (77.9% of theory) of thetetraglycidyl compound of epoxide content of 3.81 equivalents/kg (81.5%of theory); the compound softens at 103° C (Kofler).

EXAMPLE 16 Polyglycidyl compound of the product according to Example Q

The following are reacted as in Example 1: 210 g of the adduct fromExample Q (0.2 mol), 1,520 g of epichlorohydrin (16.4 mols), 8 g of 50%strength aqueous tetramethylammonium chloride and 151 g of 50% strengthaqueous sodium hydroxide solution (1.89 mols).

After the customary working up, 79 g of the viscous polyglycidylcompound are obtained, which according to the epoxide content (5.08equivalents/kg) on average contain 7.98 epoxide groups per molecule(theory: 8.0).

EXAMPLE 17 Glycidylation of the adduct manufactured according to ExampleR

736 g of the adduct manufactured according to Example R, having anepoxide content of 2.49 equivalents/kg (1 mol), are reacted with 2,738 gof epichlorohydrin and 10 g of 50% strength aqueous tetraethylammoniumbromide, the procedure according to Example 1 being followed, and thedehydrohalogenation being carried out with 197 g of 50% strength aqueoussodium hydroxide solution, in the manner described above.

Working up also takes place according to Example L, and 302.3 g (36.3%of theory) of a clear, yellow resin of medium viscosity, of which theepoxide content corresponds to 4.68 equivalents/kg (97.5% of theory),are obtained.

EXAMPLE 18 Glycidylation of the adduct manufactured according to ExampleS

The following are reacted analogously to the description in Example L:750 g of the adduct according to Example S (1 mol), 4,163 g ofepichlorohydrin (45 mols), 20 g of tetraethylammonium chloride (50%strength, aqueous), and 400 g of 50% strength sodium hydroxide solution(5 mols).

Working up also takes place according to Example L and 810 g (97.2% oftheory) of a highly viscous resin of epoxide content 4.07 equivalents/kg(84.8% of theory) are obtained.

B. EXAMPLES OF APPLICATIONS EXAMPLE I

48 parts of the epoxide resin manufactured according to Example 4, with4.69 epoxide equivalents/kg, are mixed with 55 g of hexahydrophthalicanhydride and stirred at 95° C to give a homogeneous melt. This mixtureis poured into aluminium moulds of 4 mm wall thickness which have beenprewarmed to 100° C and is cured in 6 hours at 100° C and 2 hours at120° C and 10 hours at 140° C. Mouldings having the following propertiesare obtained:

    ______________________________________                                        Flexural strength                                                                          (VSM 77,103)                                                                              15.8 - 16.8 kp/mm.sup.2                              Deflection   (VSM 77,103)                                                                               6 - 11 mm                                           ______________________________________                                    

EXAMPLE II

64 parts of the tetraglycidyl compound manufactured according to Example8), containing 4.35 epoxide equivalents/kg, are mixed with 37 parts ofhexahydrophthalic anhydride at 80° C and the mixture is cured in analuminium mould of 4 mm wall thickness in 4 hours at 120° C and 15 hoursat 150° C. A clear, transparent moulding having the following propertiesis obtained:

    ______________________________________                                        Flexural strength                                                                           (VSM 77,103) 15.8 - 17.2 kp/mm.sup.2                            Deflection    (VSM 77,103)  8 - 10 mm                                         Impact strength                                                                             (VSM 77,105) 13.3 cmkp/cm.sup.2                                 Heat distortion point                                                         according to Martens                                                                        (DIN 54,458) 99° C                                       Water absorption                                                                            (4 days/20° C)                                                                       0.3 - 0.4 %                                       ______________________________________                                    

EXAMPLE III

100 parts of the epoxide resin obtained according to Example 11 aremixed with 75 parts of hexahydrophthalic anhydride at 80° C to give ahomogeneous melt and the mixture is cured in an aluminium mould (4 mmsheets) in 4 hours/80° C an 16 hours/140° C. The mouldings thus obtainedhave the following mechanical properties:

    ______________________________________                                        Flexural strength                                                                           (VSM 77,103)  16 kp/mm.sup.2                                    Heat distortion point                                                         according to Martens                                                                        (DIN 54,458) 146 - 147° C                                Water absorption                                                                            (4 days/20° C)                                                                       0.65 %                                            ______________________________________                                    

EXAMPLE IV

100 parts of the epoxide resin manufactured according to Example 11 areprocessed with 75 parts of hexahydrophthalic anhydride as described inExample III, and the mouldings obtained show the following properties:

    __________________________________________________________________________    Flexural strength                                                                         (VSM 77,103)                                                                            14 - 36 (mean value from 5                                                   measurements = 24) kp/mm.sup.2                           Heat distortion point                                                         according to Martens                                                                      (DIN 54,458)                                                                           119 - 122° C                                      Water absorption                                                                          (4 days/20° C)                                                                  0.6 %                                                    __________________________________________________________________________

EXAMPLE V

100 parts of epoxide resin from Example 9 are treated with 70 parts ofhexahydrophthalic anhydride according to Example III. Castings havingthe following properties are obtained:

    ______________________________________                                        Flexural strength                                                                            (VSM 77,103)                                                                               23.0 kp/mm.sup.2                                  Heat distortion point                                                         according to Martens                                                                         (DIN 54,458)                                                                              125 - 126° C                                Water absorption                                                                             (4 days/20° C)                                                                      0.44 %                                                           (1 hour/100° C)                                                                     0.41 %                                            ______________________________________                                    

What we claim is:
 1. A polyglycidyl compound of the formula ##STR26##wherein B denotes the radical ##STR27## R¹ denotes a divalent radical ofthe formula ##STR28## wherein a and b are identical or different anddenote either 0 or 1;R³ is hydrogen or methyl; and R² denotes one of theradicals ##STR29##